Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H_(2)production by electrochemical water splitting,but it remains a great challenge.Herein,we reported two kinds o...Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H_(2)production by electrochemical water splitting,but it remains a great challenge.Herein,we reported two kinds of Mo O_(3)-polyoxometalate hybrid nanobelt superstructures(MoO_(3)-POM HNSs,POM=PW_(12)O_(40)and Si W_(12)O_(40))using a simple hydrothermal method.Such superstructure with highly uniform nanoparticles as building blocks can expose more surface atoms and emanate increased specific surface area.The incorporated POMs generated abundant oxygen vacancies,improved the electronic mobility,and modulated the surface electronic structure of MoO_(3),allowing to optimize the H^(*)adsorption/desorption and dehydrogenation kinetics of catalyst.Notably,the as-prepared MoO_(3)-PW_(12)O_(40)HNSs electrodes not only displayed the low overpotentials of 108 mV at 10 mA/cm^(2)current density in 0.5 mol/L H_(2)SO_(4)electrolyte but also displayed excellent long-term stability.The hydrogen evolution reaction(HER)performance of MoO_(3)-POM superstructures is significantly better than that of corresponding bulk materials MoO_(3)@PW_(12)O_(40)and Mo O_(3)@Si W_(12)O_(40),and the overpotentials are about 8.3 and 4.9 times lower than that of single Mo O_(3).This work opens an avenue for designing highly surface-exposed catalysts for electrocatalytic H_(2)production and other electrochemical applications.展开更多
Oxygen evolution reaction(OER) is one of the most important half-reactions related to metal-air batteries,fuel cells, and water-splitting. Due to the sluggish kinetic and multi-electron transfer, catalysts appear to b...Oxygen evolution reaction(OER) is one of the most important half-reactions related to metal-air batteries,fuel cells, and water-splitting. Due to the sluggish kinetic and multi-electron transfer, catalysts appear to be particularly important for the OER. Knowing the reaction mechanism is fundamental to developing new catalysts and improving OER efficiency. In this work, phase transition and atomic reconstruction on Co O(111) plane were revealed through ex-situ diffraction methods and X-ray absorption spectroscopy.At the same time, the electronic state evolution of Co(Ⅱ)/Co(Ⅲ) during the OER process has also been concluded by analyzing the magnetic properties. This work shows that during the OER process, Co(Ⅲ)experiences surface electron rearrangement from IS(intermediate-spin state) to LS(low-spin state) and then returns to IS/HS(high-spin state) under high voltage region. This work provides a new view to reveal the reaction mechanism through the magnetic property and it can be extended to more magnetic 3d transition metals for future catalyst design.展开更多
An artificial solid electrolyte interphase(SEI)with lithiophilic sites and chemical bonds anchoring lithium polysulfides(LiPSs)has been developed as a potential solution to protect the lithium(Li)metal anode of Lithiu...An artificial solid electrolyte interphase(SEI)with lithiophilic sites and chemical bonds anchoring lithium polysulfides(LiPSs)has been developed as a potential solution to protect the lithium(Li)metal anode of Lithium-sulfur(Li-S)batteries.This strategy aims to guide consistent Li deposition and relieve lithium corrosion.Herein,the evolution process of lithiophilic sites based on aluminum fluoride(AlF_(3))in an artificial SEI is disclosed in Li-S batteries with metal-based lithiophilic sites.The polyester polymer(PMMA and PPC)/AlF_(3) artificial SEI(MPAF-SEI)was homogeneously anchored on Li anode by in-situ polymerization.The conversion of AlF_(3) into Li-Al and LiF lithiophilic sites effectively reduce the Li nucleation overpotential and prevents the formation of Li dendrites.At the same time,the polymer can anchor LiPSs by chemical bonds and prevents Li corrosion.The optimized MPAF-SEI protected Li demonstrates excellent stability for over 3000 h at a capacity of 1 mAh cm^(-2) in Li||Li symmetric cells.The Li-S battery with low N/P(4)exhibits a capacity of 532.6 mAh g^(-1) over 300 cycles lifespan at 0.5 C.展开更多
Rationally designed novel cost-effective hydrogen evolution reaction(HER)electrocatalysts with controlled surface composition and advanced structural superiority is extremely critical to optimize the HER performance.P...Rationally designed novel cost-effective hydrogen evolution reaction(HER)electrocatalysts with controlled surface composition and advanced structural superiority is extremely critical to optimize the HER performance.Polyoxometalates(POMs)with structural diversity and adjustable element compositions represent a promising precursor for rational design and preparation of HER electrocatalysts.Herein,a series of transition metal-doped MoS_(2)materials with different surface engineered structures(Fe,Cr,V doping and S vacancies)(M-MoS_(2)/CC,M=Fe,Cr and V)were fabricated by a simple hydrothermalvulcanization strategy using Keplerate polyoxomolybdate nanoball({Mo_(72)Fe_(30)},{Mo_(72)Cr_(30)},{Mo_(72)V_(30)},{Mo_(132)})as precursors.The enlarged interlayer spacing as well as the integration of homogeneous transition metal doping and abundant sulfur vacancies endows prepared M-MoS_(2)/CC with superior HER electrocatalytic performance and excellent long-term working stability in both acidic and alkaline media.The optimized Fe-MoS_(2)/CC afford current densities of 10 and 50 mA/cm^(2)at overpotentials of 188/272 mV and 194/394 mV in 0.5 mol/L H_(2)SO_(4)and 1.0 mol/L KOH aqueous solution,respectively,outperforming most of reported typical transition metal sulfide-based catalysts.This work represents an important breakthrough for POMs-mediated highly efficient transition metal sulfide-based HER electrocatalysts with wide range pH activity and may provide new options for the rational design of promising HER electrocatalysts and beyond.展开更多
LiBr as a promising redox mediator(RM)has been applied in Li-O_(2)batteries to improve oxygen evolution reaction kinetics and reduce overpotentials.However,the redox shuttle of Br_(3)^-can induce the unexpected reacti...LiBr as a promising redox mediator(RM)has been applied in Li-O_(2)batteries to improve oxygen evolution reaction kinetics and reduce overpotentials.However,the redox shuttle of Br_(3)^-can induce the unexpected reactions and thus cause the degradation of LiBr and the corrosion of Li anode,resulting in the poor cyclability and the low round-trip efficiency.Herein,MgBr_(2)is firstly employed with dual functions for Li-O_(2)batteries,which can serve as a RM and a SEI film-forming agent.The Br^(–)is beneficial to facilitating the decomposition of Li_(2)O_(2)and thus decreasing the overpotential.Additionally,a uniform SEI film containing Mg and MgO generates on Li anode surface by the in-situ spontaneous reactions of Mg^(2+)and Li anode in an O_(2)environment,which can suppress the redox shuttle of Br_(3)^-and improve the interface stability of Li anode and electrolyte.Benefiting from these advantages,the cycle life of Li-O_(2)battery with MgBr_(2)electrolyte is significantly extended.展开更多
基金financially supported by the Program for the Development of Science and Technology of Jilin Province(Nos.YDZJ202201ZYTS313,YDZJ202201ZYTS395,20240402072GH,and 20240101004JJ)the National Natural Science Foundation of China(Nos.22201097 and 52171210)。
文摘Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H_(2)production by electrochemical water splitting,but it remains a great challenge.Herein,we reported two kinds of Mo O_(3)-polyoxometalate hybrid nanobelt superstructures(MoO_(3)-POM HNSs,POM=PW_(12)O_(40)and Si W_(12)O_(40))using a simple hydrothermal method.Such superstructure with highly uniform nanoparticles as building blocks can expose more surface atoms and emanate increased specific surface area.The incorporated POMs generated abundant oxygen vacancies,improved the electronic mobility,and modulated the surface electronic structure of MoO_(3),allowing to optimize the H^(*)adsorption/desorption and dehydrogenation kinetics of catalyst.Notably,the as-prepared MoO_(3)-PW_(12)O_(40)HNSs electrodes not only displayed the low overpotentials of 108 mV at 10 mA/cm^(2)current density in 0.5 mol/L H_(2)SO_(4)electrolyte but also displayed excellent long-term stability.The hydrogen evolution reaction(HER)performance of MoO_(3)-POM superstructures is significantly better than that of corresponding bulk materials MoO_(3)@PW_(12)O_(40)and Mo O_(3)@Si W_(12)O_(40),and the overpotentials are about 8.3 and 4.9 times lower than that of single Mo O_(3).This work opens an avenue for designing highly surface-exposed catalysts for electrocatalytic H_(2)production and other electrochemical applications.
基金financially supported by the National Natural Science Foundation of China(No.52171210)the Program for the Development of Science and Technology of Jilin Province(Nos.20240101004JC,20220201130GX,and 20240402072GH)。
文摘Oxygen evolution reaction(OER) is one of the most important half-reactions related to metal-air batteries,fuel cells, and water-splitting. Due to the sluggish kinetic and multi-electron transfer, catalysts appear to be particularly important for the OER. Knowing the reaction mechanism is fundamental to developing new catalysts and improving OER efficiency. In this work, phase transition and atomic reconstruction on Co O(111) plane were revealed through ex-situ diffraction methods and X-ray absorption spectroscopy.At the same time, the electronic state evolution of Co(Ⅱ)/Co(Ⅲ) during the OER process has also been concluded by analyzing the magnetic properties. This work shows that during the OER process, Co(Ⅲ)experiences surface electron rearrangement from IS(intermediate-spin state) to LS(low-spin state) and then returns to IS/HS(high-spin state) under high voltage region. This work provides a new view to reveal the reaction mechanism through the magnetic property and it can be extended to more magnetic 3d transition metals for future catalyst design.
基金supported by the Jilin Province Science and Technology Department Program(Nos.YDZJ202201-ZYTS304,20220201130GX and 20240101004JJ)the National Natural Science Foundation of China(Nos.52171210 and 52471229)the Science and Technology Project of Jilin Provincial Education Department(No.JJKH20220428KJ).
文摘An artificial solid electrolyte interphase(SEI)with lithiophilic sites and chemical bonds anchoring lithium polysulfides(LiPSs)has been developed as a potential solution to protect the lithium(Li)metal anode of Lithium-sulfur(Li-S)batteries.This strategy aims to guide consistent Li deposition and relieve lithium corrosion.Herein,the evolution process of lithiophilic sites based on aluminum fluoride(AlF_(3))in an artificial SEI is disclosed in Li-S batteries with metal-based lithiophilic sites.The polyester polymer(PMMA and PPC)/AlF_(3) artificial SEI(MPAF-SEI)was homogeneously anchored on Li anode by in-situ polymerization.The conversion of AlF_(3) into Li-Al and LiF lithiophilic sites effectively reduce the Li nucleation overpotential and prevents the formation of Li dendrites.At the same time,the polymer can anchor LiPSs by chemical bonds and prevents Li corrosion.The optimized MPAF-SEI protected Li demonstrates excellent stability for over 3000 h at a capacity of 1 mAh cm^(-2) in Li||Li symmetric cells.The Li-S battery with low N/P(4)exhibits a capacity of 532.6 mAh g^(-1) over 300 cycles lifespan at 0.5 C.
基金financially supported by the National Natural Science Foundation of China(Nos.52171210,21978110 and 22201097)the Program for the Development of Science and Technology of Jilin Province(Nos.20220201130GX and YDZJ202201ZYTS313)。
文摘Rationally designed novel cost-effective hydrogen evolution reaction(HER)electrocatalysts with controlled surface composition and advanced structural superiority is extremely critical to optimize the HER performance.Polyoxometalates(POMs)with structural diversity and adjustable element compositions represent a promising precursor for rational design and preparation of HER electrocatalysts.Herein,a series of transition metal-doped MoS_(2)materials with different surface engineered structures(Fe,Cr,V doping and S vacancies)(M-MoS_(2)/CC,M=Fe,Cr and V)were fabricated by a simple hydrothermalvulcanization strategy using Keplerate polyoxomolybdate nanoball({Mo_(72)Fe_(30)},{Mo_(72)Cr_(30)},{Mo_(72)V_(30)},{Mo_(132)})as precursors.The enlarged interlayer spacing as well as the integration of homogeneous transition metal doping and abundant sulfur vacancies endows prepared M-MoS_(2)/CC with superior HER electrocatalytic performance and excellent long-term working stability in both acidic and alkaline media.The optimized Fe-MoS_(2)/CC afford current densities of 10 and 50 mA/cm^(2)at overpotentials of 188/272 mV and 194/394 mV in 0.5 mol/L H_(2)SO_(4)and 1.0 mol/L KOH aqueous solution,respectively,outperforming most of reported typical transition metal sulfide-based catalysts.This work represents an important breakthrough for POMs-mediated highly efficient transition metal sulfide-based HER electrocatalysts with wide range pH activity and may provide new options for the rational design of promising HER electrocatalysts and beyond.
基金supported by the National Natural Science Foundation of China(Nos.21978110 and 52171210)the Jilin Province Science and Technology Department Program(Nos.YDZJ202101ZYTS047,20220201130GX and 20200201187JC)the Science and Technology Project of Jilin Provincial Education Department(No.JJKH20210444KJ)。
文摘LiBr as a promising redox mediator(RM)has been applied in Li-O_(2)batteries to improve oxygen evolution reaction kinetics and reduce overpotentials.However,the redox shuttle of Br_(3)^-can induce the unexpected reactions and thus cause the degradation of LiBr and the corrosion of Li anode,resulting in the poor cyclability and the low round-trip efficiency.Herein,MgBr_(2)is firstly employed with dual functions for Li-O_(2)batteries,which can serve as a RM and a SEI film-forming agent.The Br^(–)is beneficial to facilitating the decomposition of Li_(2)O_(2)and thus decreasing the overpotential.Additionally,a uniform SEI film containing Mg and MgO generates on Li anode surface by the in-situ spontaneous reactions of Mg^(2+)and Li anode in an O_(2)environment,which can suppress the redox shuttle of Br_(3)^-and improve the interface stability of Li anode and electrolyte.Benefiting from these advantages,the cycle life of Li-O_(2)battery with MgBr_(2)electrolyte is significantly extended.
